Morpholides of mixtures of epoxidized, saturated, and polyunsaturated fatty acids



Agni 23, 1968 F. c. MAGNE ET AL 3,379,551

MORPHOLIDES OF MIXTURES OF EPOXIDIZED, SATURATED, AND

POLYUNSATURATED FATTY ACIDS Original Filed Jan. 15, 1962 INVENTORS FRANKC. MAGNE EVALD L. SKAU ROBERT R. MOD

BY a I. I f

I ATTORNEY United States Patent MORPHOLIDES OF MIXTURES 0F EPQXHDEZED,SATURATED, AND POLYUNSATURATED FATTY ACIDS Frank Magne, Evald L. Sitau,and Robert R. Mod, New ()rleans, La, assignors to the United States ofAmerica as represented by the Secretary of Agriculture Originaiappiication Jan. 15, 1962, Ser. No. 166,742, new Patent No. 3,219,664,dated Nov. 2.3, 1965. Divided and this application Apr. 2, 1965. Ser.No. 445,234

1 Ciairn. (Cl. 106-616) This application is a division of applicationSer. No. 166,742, filed Ian. 15, 1962, now US. Patent No. 3,219,664.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmermet.

This invention relates to unique mixed morpholides. More particularly,the invention provides the morpholides of mixtures of long chainsaturated and unsaturated fatty acids and the epoxy derivatives thereofthat can reproducibly be produced from the fatty acids found in naturalglycerides. These mixed morpholides are efficient primary solventplasticizers exhibiting good compatibility with polymers and copolymersof vinyl chloride.

A morpholide of an acid is an amide of the acid in which the amidonitrogen atom is a nitrogen atom of a morpholine ring. Prior workershave produced the morpholides and other amides of various individualfatty acids and mixtures of fatty acids. Many of the fatty acid amidesheretofore produced, e.g., those disclosed in US. Patents 1,986,854;2,339,056; and 2,380,925; are solvent plasticizers for hydrophilic vinylresins, such as the polyvinyl acetal resins.

A compound which is a solvent plasticizer for, and thus is compatiblewith, a hydrophilic vinyl resin such as a polyvinyl acctal resin,exhibits only a very limited compatibility with a hydrophobic vinylresin such as a polyvinyl chloride. If a resin is plasticized with acompound with which it has only a limited compatibility the plasticizersoon exudes or migrates to the surface unless the plasticizer is used inlimited amount or is used in conjunction with a mutual solvent, toobtain adequate compatibility.

' As might be expected from the known compatibility of variousmorpholides of fatty acids with the polyvinyl acetals, the morphoiidemixtures from glyceride oil acids such as cottonseed oil acids or peanutoil acids, although in other respects satisfactory vinyl chloride resinplasticizers, are highly incompatible with polymers of vinyl chloride,even when used as a secondary plasticizer with an equal amount of ahighly capatible plasticizer.

Similarly, the morpholide of palmitic acid and the morpholide of stearicacid, though in other respects satisfactory vinyl chloride plasticizers,have been found to be highly incompatible when used as plasticizers forvinyl chloride resins, exhibiting migration to the surface within 36hours.

The term vinyl chloride resins is used throughout the specification andclaims to refer to polymers and copolymers of monomers containing vinylchloride in a predominant proportion in parts by weight. Terms such asgood compatibility, compatible, and compatible plasticizers in referenceto plasticizers for vinyl chloride resins are used throughout thespecification to refer to plasticizers which show no signs of exudationor migration to the surface for at least days when the plasticizer ispresent in the proportion of about 70 parts per parts by Weight of vinylchloride resin.

The primary object of the present invention is to provide mixedmorpholides which are good primary solvent plasticizers for vinylchloride resins, and which are plasticizers that can economically beproduced from fatty acids obtainable from glyceridic oils and fats.

The mixed morpholides provided by this invention exhibit goodcompatibility with polymers and copolymers of monomers predominating invinyl chloride, such as polyvinyl chloride, and the vinyl chloride-vinylacetate copolymers predominating in vinyl chloride. They may be employedas plasticizers in proportions of from 10 to about 70 parts by weightper 100 parts by weight of polymer. Their plasticizing efficiency ishigh and the resulting plasticized resins have good thermal and lightstability, good low-temperature properties, and a low volatility loss.

In US. Patent No. 2,863,845 it was disclosed that the morpholides ofmixed saturated and unsaturated vegetable oil fatty acids in whichmixture of acids the weight proportions of saturated acids (5),monoolefinic acids (M), polyolefinic acids (P), and epoxidized fattyacids (E), are such that S/S+M+P+E is from about and P/M+P +E is lessthan about the value of E being zero when no epoxidized fatty acids arepresent in the fatty acid mixture, are good compatible plasticizers forvinyl chloride resins. The term epoxidized fatty acids is used todesignate C to C alkanoic and alkenoic acids containing at least oneepoxy group. Such acids are produced by the epoxidation of at least oneolefinic group of an unsaturated fatty acid.

In copending patent application Ser. No. 79,470 filed Dec. 29, 1960, andnow U.S. Patent No. 3,066,111, it was further disclosed that themorpholide mixtures obtained by reacting morpholine with mixtures of thefatty acids which occur in selectively hydrogenated cottonseed oil, saidmorpholide mixtures containing a proportion of saturated,monounsaturated, and polyunsaturated acyls; i.e. acyls obtainable fromselectively hydrogenated cottonseed oil, such that the acyls areequivalent to a mixture of acids in which S/S-l-M+P is about and P/M+Pis less than A are good compatible plasticizers for vinyl chlorideresins.

We have now made the surprising discovery that morpholide mixtures ofmorpholides of vegetable oil fatty acids containing a proportion ofsaturated, monounsaturated, and polyunsaturated acyls such that the acylmixture is equivalent to a mixture of acids in which P/M+P is muchlarger than are compatible plasticizers for vinyl resins provided thevalue of S/S-|-M+P lies within a specified range which depends on thevalue of P/M-l-P and provided also that the saturated acyls present inthe morpholide mixture are predominantly saturated acyls containing from12 to 18 carbon atoms and that the percentage of saturated acylscontaining 18 or more carbon atoms in the morpholide mixture amounts toless than about 17% of all the acyls in the morpholide mixture. Forexample, as can be seen from the examples and the figure (in whichfigure, as described below, all compositions within the approximateboundaries of area Mfgc are compatible), morpholide mixtures ofsaturated, monounsaturated, and polyunsaturated morpholides for whichP/M-l-P (represented by the compositions along the straight line joiningx and S) are compatible only between 1' and 11; that is, only if thevalue of S/S+M+P lies between about and and provided [also that thesaturated acyls present in the morpholide mixture are predominantlysaturated acyls containing from 12 to 18 carbon atoms, and that thepercentage of saturated acyls containing 18 or more carbon atoms in themorpholide mixture amounts to less than about 17% of all the acyls inthe morpholide. This is surprising since, as is obvious from the figure,such as compatible plasticizing mixtures can be prepared by mixing twoincompatible plasticizers; i.e., for example, by mixing equal weights ofthe compositions represented by S and x, each of which is incompatible,or in general, by mixing the compositions represented by S and x in anyproportion between about 1 and 6 parts by weight of x to 4 parts byweight of S.

Similarly we have also discovered that morpholide mixtures ofmorpholides of vegetable oil fatty acids in which S/S-l-M-l-P is muchlarger than are compatible vinyl plasticizers provided the ratio P/M+Plies within a specified range of values and provided also that thesaturated acyls present in the morpholide mixture are predominantlysaturated acyls containing from 12 to 18 carbon atoms and that thepercentage of saturated acyls con taining 18 or more carbon atoms in themorpholide mixture amounts to less than about 17% of all the acyls inthe morpholide mixture. This is surprising since it shows, as can beseen from the figure, that compatible plasticizers represented by thecompositions within area Mfgc can be obtained by mixing (in appropriateproportions) two incompatible plasticizers, e.g., those represented bycompositions in areas Mrfa and cgS, respectively.

We have also discovered that morpholide mixtures of the morpholides ofsaturated, polyunsaturated, and epoxidized fatty acids in whichS/S-l-M-i-P-l-E is much larger than W and P/M-l-PIE is much larger thanbut which are compatible vinyl chloride resin plasticizers can be madeby mixing two incompatible morpholide mixtures, provided that thesaturated acyls present in the morpholide mixture are predominatelysaturated acyls containing from 12 to 18 carbon atoms, and that thepercentage of saturated acyls containing 18 or more carbon atoms in themorpholide mixture amounts to less than about 17% of all the acyls inthe morpholide mixture. For example, the composition represented byExample 43, for which P/M+P+E about and the composition represented byExample 40, for which S/S-i-Md P-l-E about 7 are individuallyincompatible, but a mixture of equal parts of these compositions(Example 46), for which E/E+S:5"/1OQ and is compatible.

The mixed morpholides of this invention comprise morpholide mixtures ofthe morpholides of mixed saturated and unsaturated fatty acids, in whichmixture of acids, the weight proportions of saturated acids (S),monoolefinic acids (M), and polyolefinic acids (P), are such that thefollowing conditions are satisfied: (1) that S/S-i-P is greater thanabout 9 0 (i.e., that the composition lies within area M68 in thefigure), (2) that M/SlM-|-P is greater than about 9 (i.e., that thecomposition lies within area Mbc), and (3) that P/M|P is less than about93 (i.e., that the composition lies within area MaS), excluding thosemixtures which are such that S/S-l-M-l-P is either less than about X orequal to about and P/M-l-P is less than about A0 (i.e., excludingcompositions lying within the area Mrk or on the line ny); provided alsothat. the saturated acyls present in the morpholide mixture arepredominantly saturated acyls containing from 12 to 18 carbon atoms, andthat the percentage of saturated acyls containing 1 8 or more carbonatoms in the morpholide mixture amounts to less than about 17% of allthe acyls in the morpholide mixture. Thus, the mixed morpholides of thisinvention comprise compositions represented by all compositions withinthe area krfgc in the figure, except along ny; that is, the area whichis common to the areas MeS, Mbc, and MaS, excluding those within thearea Mrk and along line my.

The morpholides of this invention also include the morpholides ofepoxidized fatty acids. They also include the morpholides of mixtures ofepoxidized fatty acids with saturated acids and/ or polyunsaturatedfatty acids in which mixtures of acids, the weight proportions ofsaturated acids (S), epoxidized acids (E), and polyunsaturated acids(P), are such that the following conditions are satisfied: (1) thatE/S+E is greater than about 9 (2) that E/P-l-E is greater than about and(3) that the saturated acids present in the mixture of acids arepredominantly saturated acids containing from 12 to 18 carbon atoms andthe percentage of saturated acids containing 18 or more carbon atoms insaid mixture of acids is less than about 17% of all the acids in themixture.

While the morpholides of this invention can be produced in a variety ofways, they are preferably produced by reacting the mixed acids withmorpholine. The mixed acids are preferably produced by saponifying anatural glyceride, acidifying the resulting salts and, if necessary,adjusting the composition of the resulting acid mixture so as to obtaina suitable composition which when reacted with morpholine will result ina compatible plasticizer (l) by known procedures for reducing theproportion of saturated acyls such as fractional crystallization ordistillation, and/or (2) converting polyunsaturated acyls tomonounsaturated acyls, epoxyalkenoic acyls or epoxyalkanoic acyls-thecorresponding morpholides of which are themselves compatibleplasticizerssuch as by hydrogenation, halogenation, formylation,dimerization, or epoxidation, etc., and/or (3) by admixing with otherfatty acid mixtures and/ or with pure fatty acids. Alter n-atively, thefractionation, hydrogenation, epoxidation or mixing, etc., may beperformed on the materials separately or combined which are capable ofyielding the desired acid composition or on the correspondingmorpholides or mixed morpholides. In general, it is usually preferred toperform epoxidation at the morpholide stage.

The necessary adjustment can readily be deduced from the figure and froma knowledge of the proportions of S, M, and P acyls in the given mixtureas determined by standard analytical procedures. For example, consider amixture of vegetable oil fatty acids in which the weight proportions aresuch that S/S-i-P is about P/M+P is about M/S+M+P is about and in whichthe predominant saturated fatty acid is the C acid with very smallamounts of the C and C acids. The figure shows that the mixedmorpholides made from this mixture (represented approximately by w inthe figure) would be incompatible. The figure also shows that thismixture of fatty acids can be readily converted to a suitable mixture ofacids (i.e., to a composition represented by points within area Mfgc),which when reacted with morpholine will result in a compatibleplasticizer; for example, by converting some or all of thepolyunsaturated acyls to monounsaturated acyls by such procedures ashydrogenation, halogenation, forrnylation, dimerization, m-aleinationetc., so that S/S+P is greater than about 9 M/S-l-M-l-P is greater thanabout 91 and P/M-l-P is less than about 9 The composition of themorpholide mixtures of this invention which contain no epoxidized acylsare represented by all compositions within the area Mfgc in the figure;that is, within the area bounded approximately by M fg, and go. Theboundaries Mf, fg, and gc are only approximate. Thus the composition ofExample 10 which lies near the boundary outside this area wascompatible. Slightly incompatible compositions lying close to butoutside the boundaries Mf, fg, and go and even less compatiblecompositions may be used satisfactorily as primary plasticizers inpolyvinyl chloride resin formulations containing lower percentages ofplasticizer and/or as secondary plasticizers admixed with a suitablecompatibilizing plasticizer such as the morpholide of epoxidized fattyacids or compatible mixtures of the morpholides of epoxidized fattyacids and/ or monounsaturated fatty acids and/ or polyunsaturated fattyacids and/ or saturated fatty acids. Similarly incompatible morpholidemixtures containing the morpholides of epoxidized fatty acids can beused as secondary plasticizers with compatible morpholide compositionswhich lie within the area Mfgc in the figure.

The proportion of saturated fatty acyls having 18 or more carbon atomsin the chain which can be present in the saturated acyl fraction withoutcausing incompatibility will vary with the overall composition of themorpholide mixture particularly the relative proportions of saturated,monounsaturated, and polyunsaturated acyls present in the mixture. Itcan be determined for a given overall composition by evaluating theperformance of a series of samples which differ only in the proportionof the C or longer-chain saturated fatty acyls in the saturated fattyacyls present.

We have also discovered that the morpholides of epoxidized fatty acids,i.e., of C to C alkanoic or alkenoic acids containing at least one epoxygroup, are compatible, highly efficient, primary plasticizers for vinylchloride resins and impart to the plasticized resin a high degreeVarious morpholide mixtures were tested as plasticizers for vinylchloride-vinyl acetate (95-5) copolymer resin (Vinylite VY DR) in astandard formulation comprising: 63.5% of Vinylite VYDR, 35%plasticizer, 0.5% stearic acid, and 1.0% basic lead carbon-ate. Thisformulation for each morpholide sample was milled, molded, and tested.In all examples, the sample was rated as incompatible if the moldedstock showed any evidence of exudation or migration .to the surfaceduring a shelf storage of days.

The morpholide mixtures used in Examples 1 to 19 were ternarycompositions prepared by mixing appropriate proportions of themorpholide of oleic acid, the morpholide of linoleic acid, and themorpholide of palmitic acid. The approximate compositions and theresults of the compatibility test for these samples are given in Table Iand plotted as points in the ternary weight-composition diagram in thefigure. In this figure compatible morpholide mixtures are represented byopen circles and incompatible mixtures by black circles. In Table I, M,S, and P represent the weight percent of the morpholides of oleic,palmitic, and linoleic acids comprising the morpholide mixture,respectively.

TABLE I Example N0. M, S, P, M/ P/M-l-P S/S-l-P Compat- Percent PercentPercent S+M+P ibility 1 51.2 47.7 1.1 51/100 2/100 98/100 0 78.6 14. 56. 8 79/100 8/100 68/100 0 71. 4 19. 2 9. 3 71/10 12/100 07/100 0 80. 79. 8 9. 5 81/100 11/100 51/100 0 37.2 01.9 0.8 37/100 2/100 99/100 0 45.0 38.4 16. 5 45/100 27/100 70/100 0 45. 5 42. 0 12. 3 46/100 21/10077/100 0 35. 1 43. 2 21. 5 /100 38/100 67/100 0 26. 3 57. 4 16.1 26/10038/100 78/100 0 53. 8 24. 2 21. 9 54/100 20/100 52/100 0 03. 0 19. 3 16.9 64/100 21/100 53/100 0 70. 0 11.2 18. 8 70/100 21/100 37/100 I 70. 015. 0 15. 0 70/100 18/100 50/100 0 43. 4 36. O 20. 6 43/100 32/10064/100 0 45. 3 40.1 14. 6 45/100 24/100 73/100 0 40.5 30. 0 29. 5 41/10042/100 /100 1 30. 0 69. 5 0. 5 30/100 2/100 99/100 0 25.0 74. 6 0. 425/100 2/100 99/100 I 1 C Compatible; I=Incompatible.

of stability against heat and light. They are efiicient stabilizers forvinyl chloride resins. We have also discovered that morpholide mixturessuch as can be made by mixing even as much as about one part of themorpholide of palmitic acid with one part of the morpholide ofepoxidized fatty acids or by mixing as much as about 3 parts of themorpholide of polyunsaturated fatty acids with 7 parts of the morpholideof epoxidized fatty acids were also found to be compatible vinylchloride resin plasticizers and have the advantage that the plasticizedresin has increased thermal stability.

Morpholide mixtures which can be prepared by mixing in any proportionany of the compatible morpholide compositions within the area Mfgc inthe figure with either the morpholides of epoxidized fatty acids or withany mixture of morpholides of fatty acids containing the morpholide ofepoxidized fatty acids which mixture of morpholides is itself acompatible vinyl chloride plasticizer are also compatible vinyl chlorideplasticizers imparting good thermal stability to the resin. In makingsuch compatible morpholide mixtures the morpholides of epoxidized fattyacids may be introduced by addition or they may be formed in situ; forexample, by epoxidizing some of the morpholides of the monounsaturatedor polyunsaturated fatty acids in a given morpholide mixture.

The following examples numbered 1 through 46, the data for which arelisted singly in tabular form but which may be considered individuallyor in related groups for discussion purposes, will demonstrate severalof the manifold expressions of our invention.

The sample used in Example 20 was the morpholide of Armours animal typeacids (Neofat N0. 47), a mixture of fatty acids having the followingcomposition: 10% myristic, 43% palmitic, 9% stearic, 30% oleic, and 8%linoleic acids.

The sample used in Example 21 was the morpholide of Armours animal acids(Neofat No. a mixture of fatty acids having the following composition:2% myristic, 26% palmitic, 16% stearic, 48% oleic and 8% linoleic acids.

The morpholide of rapeseed fatty acids used in Example 22 was preparedfrom the composite fatty acids which were obtained by saponification andacidification of rapeseed oil and which consisted of approximately 9.6%linolenic acid, 13.3% linoleic acid, 20.4% oleic acid, 49% erucic acid,and 7.6% saturated fatty acid. The resulting morpholide mixture, forwhich the composition was such that M/S-l-M-f-P= P/M|-P= and S/S-|-P=was tested as a plasticizer for Vinylite VYDR resin was incompatible.

The morpholide sample of Example 23 was made by adjusting thecomposition of the morpholide mixture of Example 22. The latter wasmixed with an equal part by weight of a morpholide mixture thecomposition of which was such that M/S-i-M-l-P=about 7 P/M+P=about 0 andS/s-l-P about 9 resulting in a final mixture for which M/S-i-M+P=aboutP/M+P=about and S/S+P=about This was found to be a compatibleplasticizer for Vinylite VYDR resin.

The compositional data for the morpholide mixtures of Examples 20 to 23are given in Table II in which table M, S, and P, represent the weightpercent of the morpholides of monoolefinic, saturated and polyolefinicfatty acids, respectively, comprising the morpholide mixture, in whichmorpholide mixture, the saturated acyls containing 18 or more carbonatoms amount to less than about 17% of all the acyls in the morpholidemixture.

TABLE II Example M, Wt. S, Wt. I, Wt. M/ P/M-l-P S/S +P Compati- No.Percent Percent Percent S+M +P bility 1 30 02 8 30/100 21/100 89/100 4844 8 48/100 14/100 85/100 C 69. 4 7. 6 23. 0 00/100 25/100 25/100 I 72.216.3 11.5 72/100 14/100 59/100 C 1 C Compatible; I =Incompatible.

The physical properties of the Vinylite VYDR resin 25 plasticized withthe morpholide mixtures of Examples to 23 are shown in Table III.

compatible vinyl chloride plasticizer though it was made by mixing thesamples of Examples 40 and 43 both of which were incompatible.

TABLE III Example Tensile 100% Elonga- Brittle Vola- Compat- No,Plasticizer, Morpholide of Strength, Modulus, tion, Point, tilityibility 1 p.s.i. p.s.i. percent C.

20 Animal type acids 2, 940 1,390 400 30 0.62 C 21 Animal acids 2, 9501,370 390 -34 0.36 o 22.. Rapeseed oil acids 3,030 1,470 400 53 1.00 I23 Adjusted rapeseed oil acids 2,880 1, 330 360 -43 0.55 C 24 Epoxyoleicacid 3,030 1,270 360 16 0.41 G 25 Epoxystenric acid 2, 850 1, 300 350-28 0. 54 C 26. Diepoxystearic acid 2,950 1,330 350 -16 0. 49 O 27.Partially epoxidized cottonseed oil acids 2, 940 1,210 400 26 0. 73 C 23U Fully expoxidized cottonseed oil acids 2, 990 1, 310 360 22 0. 72 C 1C=Compatible; I=Incornpatible.

The corresponding data for Examples 24 to 29 are TABLE IV given inTables 111 and/or IV. For these samples, M, E S p EIE+S EIP+E c mpati-E, S, and P represent the approximate weight percent of bllltymorpholides of monoolefinic (unepoxidrzed), epoxidized, 100 0 0 100/100100/100 0 saturated and polyunsaturated acids, respectively, com- 188 gg 8 prising the morpholide mixtures, in which morpholide 50 25 Q 0mixtures the saturated acyls containing 18 or more carbon 2 g atomsamount to less than about 17% of all the acyls in 00 49 0 c themorpholide mixture. The morpholide samples of 22 g? g Examples 27 and 28were prepared by epoxidation of the 30 50 0 c morpholide of cottonseedoil fatty acids to an oxirane ggg 8 oxygen content of 2.62% and 4.07%,i.e., to an extent is 70 0 y C equivalent to that necessary to epoxidizeabout and gg f g 8 about 100%, respectively, of the total number ofdouble 31 70 8 29/1 100/100 r bonds Present 75 0 25 100/100 75/100 0 Themorpholide sample of Example 29 was prepared 52 g 20 go/igg 3 5 5 1 bymixing the proper proport1ons of the morphollde nux- 5 m 5 57/100 80/1000 ture of Example 28 and the morpholide of selectively 47.5 37.5 1556/100 76/100 0 46 0 45 37.5 17.5 54 100 72 100 0 hydrogenatedcottonseed fatty acids. The plasticized resin had a specially highdegree of thermal stability.

The morpholide mixtures used in Examples 30 to 36, for which thecompatibility data are given in Table IV, were prepared by mixing theproper proportions of the morpholides of oleic acid, epoxyoleic acid,and palmitic acid.

I The morpholide mixtures used in Examples 37, 38, 39, 40, 41, 42, and43 were binary compositions prepared by mixing appropriate proportionsof the morpholide of 1 C=Compatible; I=Incompatib1e.

2 Compositions containing the moipliolides of both monounsaturated fattyacids and epoxidized fatty acids, and which can be prepared by mixingappropriate proportions of two morpholide mixtures each of which is acompatible vinyl chloride plasticizer.

3 Compositions containing the morpholides of both monounsaturated fattyacids and e oxidized fatty acids, and which can be prepared by mixingtwo morp olide mixtures each of which is an incompatible vinyl chlorideplasticizer. For example, the sample of Example 36 can be prepared bymixing equal parts by weight of two incompatible morpholide mixtures,one consisting of 25 parts of the morpholide of a monounsaturated acidand 75 parts of the niorpholide oi palmitic acid and the otherconsisting of 35 parts of the morpholide ol epoxyoleic acid and 56 partsof the morpholide 0f palmitic acid.

We claim:

1. The morpholides of a mixture of epoxidized fatty acids, saturatedfatty acids, and polyunsaturated fatty acids in which mixture of acidsthe weight proportions of saturated acids (S), epoxidized acids ('E),and polyunsaturated acids (P), are such that all of the followingconditions are satisfied: (1) that E/S+E is greater than about 50/100;(2) that =E/P+E is greater than about 70/100; (3) that the saturatedacids present in the mixture of acids are saturated acids containingfrom 10 12 to 18 carbon atoms; and (4) that the percentage of saturatedacids containing at least 18 carbon atoms in 10 said mixture of acids isless than about 17% of all the acids in the mixture.

References Cited UNITED STATES PATENTS 12/1958 Magne et al 260-304 ALLANLIEBERMAN, Primary Examiner. MORRIS LIEBMAN, Examiner.

1. THE MORPHOLIDES OF A MIXTURE OF EPOXIDIZED FATTY ACIDS, SATURATEDFATTY ACIDS, AND POLYUNSATURATED FATTY ACIDS IN WHICH MIXTURE OF ACIDSTHE WEIGHT PROPORTIONS OF SATURATED ACIDS (S), EPOXIDIZED ACIDS (E), ANDPOLYUNSATURATED ACIDS (P), ARE SUCH THAT ALL OF THE FOLLOWING CONDITONSARE SATISIFIED; (1) THAT E/S+E IS GREATER THAN ABOUT 50/100; (2) THATE/P+E IS GRREATER THAN ABOUT 70/100; (3) THAT THE SATURATED ACIDSPRESENT IN THE MIXTURE OF ACIDS ARE SATURATED ACIDS CONTAINING FROM 12TO 18 CARBON ATOMS; AND (4) THAT THE PERCENTAGE OF SATURATED ACIDSCONTAINING AT LEAST 18 CARBON ATOMS IN SAID MIXTURE OF ACIDS IS LESSTHAN ABOUT 17% OF ALL THE ACIDS IN THE MIXTURE.